Detergent composition with siliconate-zeolite and silicate builder

ABSTRACT

The preparation and applications of anionic siliconate-zeolite composites are disclosed. The composites are formed by coating the surface of zeolite particles with an aqueous solution of an anionic functional organosiliconate. The composites are particularly useful as components of soluble silicate containing detergent compositions since they do not agglomerate with the soluble silicates to form large insoluble particulates that can deposit on fabrics during laundry. Detergent compositions containing the composites are disclosed.

BACKGROUND OF THE INVENTION

This invention relates to the field of zeolites and their use indetergent formulations. In particular, it relates to zeolites coatedwith anionic functional organosilicon compounds. The coated zeolite hasimproved properties making it more useful in detergent formulations.

Zeolites are well known ion exchange agents that have been used recentlyto replace all or part of the phosphates in several detergentformulations. However, the use of zeolites in detergents has generatedseveral problems. In particular, the zeolites tend to agglomerate duringindustrial preparation of detergent formulations. It has been suggestedthat the agglomeration results from the interaction of the zeolite withother detergent ingredients during the spray drying process. Theseagglomerates deposit on the fabric being laundered and are especiallynoticeable as white particulate material on dark fabrics.

Alkali metal silicates have been implicated as one of the components ofdetergents that may interact with zeolites to cause the agglomeration.Consequently, it has been proposed that only limited amounts ofsilicate, 3% or less, should be used in zeolite built detergents. Largeramounts of alkali metal silicate have been shown to decrease the ionexchange capacity and the rate of ion exchange of the zeolite in thedetergent. Soluble silicates, however, are valuable components indetergent formulations for their bead formation, anticorrosion and otherfunctions that make detergent processing and use easier.

U.S. Pat. Nos. 4,138,363, 4,216,125 and 4,243,545 teach that thetendency of zeolites to agglomerate during detergent processing can bereduced by treating the zeolite surface with a hydrophilic functionalsilane. While acrylates, epoxies, amines and carboxylates are suggestedas useful hydrophilic groups, the only silanes taught for treating thezeolite were beta-3,4-epoxycyclohexyl-ethyltrimethoxysilane,gamma-glycidoxypropyltrimethoxysilane andgamma-aminopropyltrimethoxysilane. However, the improvements achievedwith these silane-zeolite composites has not been sufficient to resultin commercial utilization.

Consequently there is still a need for a commercially viable way ofmodifying zeolite so that it can be incorporated in soluble silicatecontaining detergent formulations without agglomeration problems.Furthermore, it is important that the zeolite can be incorporated intothe detergent formulation without reducing its ion exchange properties.Accordingly, it is a purpose of the present invention to provide animproved method of modifying the properties of zeolite so that it can beincorporated into soluble silicate containing detergent formulationswithout producing agglomerates that deposit as white particulatematerial on fabric during laundry. It is a further object of the presentinvention to provide a zeolite that retains its capacity and rate of ionexchange when formulated in a detergent containing substantial amountsof alkali metal silicates.

SUMMARY OF THE INVENTION

The present invention provides improved detergent compositionscomprising (A) 5 to 40 percent by weight of an organic surfactantselected from the group consisting of anionic, nonionic and ampholyticsurfactants; (B) 1 to 50 percent by weight of an anionicsiliconate-zeolite composite containing zeolite with a surface coatingof 0.1 to 10 percent by weight of anionic functional siliconate; and (C)1 to 20 percent by weight of a water soluble alkali metal silicate. Theinvention further relates to the anionic siliconate-zeolite compositewhich is useful in the detergent formulations.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is based on the discovery that anionicsiliconate-zeolite composites can be prepared by contacting the zeolitewith an aqueous solution of an anionic functional siliconate andevaporating any excess water at a relatively low temperature. Theanionic siliconate-zeolite composites are especially useful in detergentformulations because they are less likely to interact with solublesilicates in the detergent to form agglomerates during processing orstorage.

The anionic siliconate-zeolite composite of the present invention can beformed with a variety of synthetic and natural zeolites. In general,synthetic zeolites are usually employed because they are more readilyavailable and are specially manufactured to have more desirable andconsistent properties. Synthetic crystalline sodium alumina silicatessuch as those described in U.S. Pat. Nos. 2,882,243, 3,012,853,3,130,007, and 3,329,628, 4,303,629 among others, are suitable to formanionic siliconate-zeolite composites. While any zeolite can be used toprepare the composite, it is usually preferred to employ zeolitesconforming to the general formula:

    Na.sub.x [(AlO.sub.2).sub.x (SiO.sub.2).sub.y ]zH.sub.2 O

where x and y are integers of at least 6; the ratio of x to y is in therange of 0.1 to 1.1; and z is an integer from about 8 to 270. Ingeneral, the water content of these zeolites is 15 to 35 percent byweight of the zeolite. Specific examples of useful zeolites includeamong others, zeolites generally conforming to the formula, Na₁₂[AlO₂)₁₂ (SiO₂)₁₂ ]20H₂ O and zeolites generally conforming to theformula Na_(x) [(AlO₂)_(x) (SiO₂)_(y) ]zH₂ O where x is an integerbetween 80 and 96 and y is an integer between 112 and 96 and z isbetween 220 and 270. Zeolites are well known in the art and have beendescribed in many patents in recent years for use as builders in laundrydetergent formulations.

The anionic siliconates used to prepare the zeolite composite areorganosilicon compounds in which the organic substituent is attached tosilicon by a silicon-carbon bond. The organic substitutent also carrisan anionic functional group which is attached to the substituent atleast 2 and preferably 3 or more carbon atoms removed from the bond tosilicon. An anionic functional group is a group that existspredominately in a disassociated ionic state in aqueous solutions andthus provides the organic substituent attached to silicon with anegative charge. Anionic functional groups can be described generally assalts of oxyacids. Anionic functional groups include salts of sulfonicacids, salts of phosphonic acid, salts of monoesters of phosphonicacids, and salts of carboxylic acids. Generally the alkali metal saltsof the acids are preferred although salts derived from other bases suchas organic quaternary ammonium hydroxide compounds can also be employedin this invention.

It should be understood that the organic substituent of the siliconatemay also contain other functionality such as ether, sulfide, hydroxy,and amine. Anionic siliconates are known materials and are describedfurther in U.S. Pat. Nos. 3,198,820, 3,816,184, 4,235,638, 4,344,860,4,352,742, 4,354,002, 4,362,644 and 4,370,255 which are herebyincorporated by reference to further illustrate the anionic functionalsiliconates and to show methods for their preparation.

The general form of the anionic siliconates can be represented by theformula:

    (MO).sub.a O.sub.(3-a)/2 Si--R--Y.sub.b

wherein R is an organic linking group wherein the anionic functionalityor any other functionality is positioned at least 2 and preferably atleast 3 carbon atoms removed from the silicon atom and Y representsanionic functional groups and b represents the number of anionicfunctional groups on the linking group and can vary from 1 to 3. In theformula, M represents the cation of a strong base such as alkali metalcations or organo quaternary ammonium cations or M represents a hydrogensuch that the siliconate also contains silanol functionality. Generallya can vary from about 1 to 3.

It is preferred that a has the value of 3 to about 2 such that theanionic siliconate is predominately a monomeric species in aqueoussolutions. Monomers are preferred because they are believed to bond morerapidly to the zeolite particle surface. It should be understood howeverthat oligomeric anionic siliconates where a is 1 to about 2 are alsouseful in the invention. Under alkaline conditions the oligomers are inequilibrium with monomers so that they can also readily bond to thezeolite surface by an equilibration process. It should also be apparentthat if desired the equilibrium can be shifted toward monomeric speciesby the addition of alkali metal hydroxide to the aqueous solution of thesiliconate.

The organic linking group, R, may contain other atoms in addition tocarbon and hydrogen such as, for example, oxygen, sulfur, and nitrogen.These atoms may be present, as other functional groups such as, forexample, ether, sulfide, hydroxy, amide, or amine. Other functionalityas represented by these exemplary atoms should be positioned at least 2and preferably 3 or more carbon atoms removed from the site of siliconatom attachment in the linking group. Such positioning of functionalitywithin the linking group provides substituents on silicon that are morestable and less readily cleaved. Generally it is preferred that thelinking group contain from 2 to a maximum of about 16 carbon atoms.While linking groups with greater than 16 carbon atoms may be used inthe invention, it is believed that the hydrophobic character produced bysuch linking groups reduce the effectiveness of the siliconates so thatlinking groups with greater than 16 carbon atoms are less preferred.

Linking groups represented by R include, among others, polyvalenthydrocarbon radicals such as dimethylene, trimethylene,hexadecamethylene, phenylene, tolylene, xenylene, naphthylene, andsubstituted polyvalent hydrocarbon radicals such as ##STR1##

Generally when M is an alkali metal cation it is preferred that it besodium because of its ready availability and low cost. Similarly, thesodium salts of the oxyacids are preferred anionic functional groups inthe siliconates.

For example anionic siliconates suitable for the present inventininclude compositions conforming generally to the formulas: ##STR2##

The anionic siliconates in which the organic substituent on siliconcontains more than one anionic functional group are preferred because oftheir more highly anionic character and because of their improvedeffectiveness in reducing the silicate induced agglomeration of zeoliteparticles. Specifically anionic functional siliconates represented bythe formula

    (MO).sub.a O.sub.(3-a)/2 Si--R--Y.sub.b

wherein b has the value 2 or 3 are preferred. One especially preferredsiliconate is represented generally by the formula ##STR3##

The anionic siliconates are water soluble materials and are usuallyprepared and stored in aqueous solutions. The water solubility andaqueous stability of the anionic siliconates greatly facilitatespreparation of the siliconate-zeolite composite. The composite can beprepared by mixing the aqueous solution of anionic siliconate with thezeolite until the solution is evenly distributed over the zeolite andthen drying the zeolite until the desired level of water content isreached. The zeolite may be slurried in aqueous solution of the anionicsiliconate or the aqueous solution of anionic siliconate may be sprayedon the zeolite powder with mixing to assure even distribution of theaqueous siliconate solution.

Generally the anionic siliconate-zeolite composite is dried only to asufficient extent to provide free flowing powders. It is not necessaryor desirable to dry the composite at temperatures above 100° C. or toremove the water of hydration of the zeolite. An advantage of theprocess of treating zeolite with anionic functional siliconate solutionsis that there is no organic solvent used or generated in the process. Incontrast, methoxy or ethoxy silane treatments generate methanol orethanol when the silane is hydrolyzed during reaction with zeolite.

In general anionic siliconate-zeolite composites containing a surfacecoating of 0.1 to 10 percent by weight of anionic functional siliconateshave been found useful in detergent formulations. While the surfacecoated zeolite has improved characteristics in regard to its tendency toagglomerate in detergent formulations, the ion exchange capacity andrate of exchange of the zeolite is essentially unchanged by the surfacecoating. The siliconate-zeolite composite may also provide improvedprocessing characteristics such as lowering the viscosity of slurries sothat higher solids content slurries can be employed in detergentmanufacture.

The detergent formulations of this invention contain from 1 to 50percent by weight of the anionic siliconate-zeolite composite. Whiledetergent compositions may contain greater than 50 percent of thecomposite, little additional benefit is derived from such high levels sothat such compositions are economically undesirable.

The detergent compositions of this invention contain 5 to 40 percent byweight of an organic detersive surfactant selected from the groupconsisting essentially of anionic, nonionic, and ampholytic surfactants.Any of the known water soluble detersive surfactants are anticipated tobe useful in the detergent compositions of this invention. Water solubledetersive surfactants include the anionics such as common soap,alkylbenzene sulfonates and sulfates, paraffin sulfonates, and olefinsulfonates; the nonionics such as alkoxylated (especially ethoxylated)alcohols and alkyl phenols, amine oxides; and the ampholytics such asthe aliphatic derivatives of heterocyclic secondary and tertiary amines.

In general, the detersive surfactants contain an alkyl group in the C₁₀-C₁₈ range; the anionics are most commonly used in the form of theirsodium, potassium, or triethanolammonium salts; and the nonionicsgenerally contain from about 3 to about 17 ethylene oxide groups. U.S.Pat. No. 4,062,647 which is hereby incorporated by reference, containsdetailed listings of the anionic, nonionic and ampholytic detersivesurfactants useful in this invention. Mixtures, especially mixtures ofC₁₂ -C₁₆ alkyl benzene sulfonates with C₁₂ -C₁₈ alcohol or alkylphenolethoxylates (EO 3-15) provide detergent compositions with exceptionallygood fabric cleaning properties.

The detergent compositions of this invention contain from 1 to 20percent by weight of a water soluble alkali metal silicate. Any of thewater soluble alkali metal silicates can be used in the detergentcompositions. Water soluble alkali metal silicates are typicallycharacterized by having a molar ratio of SiO₂ to alkali metal oxide of1.0 to 4.0. Soluble silicates are available commercially as free flowingpowders or as aqueous solutions ranging up to about 50 percent solids.The sodium silicates are usually preferred in the detergent compositionsof this invention, although potassium and lithium silicates can also beused.

The water soluble silicates are believed to perform several importantfunctions in detergent compositions. These include protection ofprocessing equipment and washing machines against corrosive action ofother detergent components, improvement of granule formation, andincreasing alkalinity and builder properties.

The detergent compositions of this invention can also contain numerousadditional detergent ingredients. Auxiliary builders such as salts ofphosphates, phosphonates, carbonates and polyhydroxysulfonates may beincluded in the detergent compositions. Organic sequestering agents suchas polyacetates, polycarboxylates, polyaminocarboxylates andpolyhydroxysulfonates can be used in the detergent compositions.Specific examples of builders and organic sequestering agents includesodium and potassium salts of tripolyphosphate, pyrophosphate,hexametaphosphate, ethylenediaminotetraacetic acid, nitrilotriaceticacid, citric acid, and citric acid isomers. Antiredeposition ingredientssuch as sodium carboxymethyl cellulose can be included to preventcertain types of soils from redepositing on clean fabric.

Other minor detergent ingredients such as suds suppressors, enzymes,optical brighteners, perfumes, anti-caking agents, dyes, colored specksand fabric softeners can also be included in the detergent compositions.

Finally bulking agents such as sodium sulfates, sodium chloride, andother neutral alkali metal salts can be added to the detergentformulation to facilitate measurement of appropriate amounts forindividual wash loads.

Any of the well known commercial methods of preparing detergentcompositions can be employed to make the detergent compositions of thisinvention. For example, the surfactant, anionic siliconate-zeolitecomposite, and alkali metal silicate can be combined in an aqueousslurry and then spray dried to provide granules. Another method involveswet mixing of the detergent components with a material that will absorbthe water and result in a free flowing granular product. Alternatively,powdered or granular components for the detergent can be selected andthey dry blended to provide the final composition.

In order that those skilled in the art may better understand how thepresent invention can be practiced, the following examples are given byway of illustration and not by way of limitation. All parts and percentsreferred to herein are by weight unless otherwise noted.

EXAMPLE 1

Three anionic siliconate-zeolite composites were prepared employingthree siliconates with different types of anionic functional groups.

Composite I was prepared by mixing a slurry of 1000 g of Na-Zeolite A (acommercially available zeolite supplied under the name Valfor® 100 by PQCorporation, Valley Forge, Pa.) and 1000 g water with 189 g of anaqueous solution of 52.7 percent anionic siliconate I which conformsgenerally to the formula ##STR4##

The slurry was heated to about 65° C. and stirred for 10 minutes. Thewater was evaporated from the slurry until a dry appearing compositecake was obtained. This material was ground to a free flowing powderform. Composite I represents a zeolite with a coating of about 9 percentsiliconate.

Composite II was prepared by forming a slurry of 1000 g of Na-Zeolite Aand 1000 g water and mixing the slurry with 195 g of an aqueous solutionof 51.4% percent anionic siliconate II which conforms generally to theformula ##STR5## The slurry was dried and ground to a free flowingpowder as described above. Composite II represents a zeolite with acoating of about 9 percent siliconate.

Composite III was prepared by forming a slurry of 1000 g of theNa-Zeolite A and 1000 g water and mixing the slurry with 14 g of anaqueous solution of 65% percent anionic siliconate III which conformsgenerally to the formula ##STR6## The slurry was dried and ground to afree flowing powder as described above. Composite III represents azeolite with a coating of about 0.9 percent siliconate.

EXAMPLE 2

This example shows that the ion exchange capacity and rate of ionexchage for zeolites coated with anionic siliconates are not adverselyaffected by the anionic siliconate coating.

A series of siliconate-zeolite composites were prepared by the method ofExample 1 using Na-Zeolite A and various coating amounts of anionicsiliconates I and II as described in Example 1. A 0.1 g portion of eachsiliconate-zeolite composite was added to a 50 ml portion of a stocksolution containing 272 ppm Ca⁺² as calcium chloride. Thesiliconate-zeolite composite was mixed in the Ca⁺² containing water forprecisely two minutes and then the mixture was quickly filtered toremove the siliconate-zeolite composite from the water. The filtrate wasthen titrated with a standard solution of ethylenediaminetetraaceticacid to determine the amount of Ca⁺² remaining in the filtrate. Theresults are presented in Table 1. The amount of Ca⁺² remaining after asimilar test employing 0.1 g of uncoated Na-Zeolite A is presented inTable 1 for comparison.

                  TABLE 1                                                         ______________________________________                                        Calcium Ion Exchange Properties                                               of Siliconate Coated Zeolite                                                                          Amount of Ca.sup.+2 Left                                         Siliconate   After Zeolite Treatment                               Anionic Siliconate                                                                       Coating Amount                                                                             (ppm)                                                 ______________________________________                                        None (control)                                                                           0            122                                                   I          1%           120                                                   I          5%            92                                                   I          10%          128                                                   II         1%           120                                                   II         5%            90                                                   II         10%          100                                                   ______________________________________                                    

EXAMPLE 3

This example illustrates the preparation of powdered detergentcompositions containing the anionic siliconate-zeolite composite.

A powder detergent composition was prepared with each of the anionicsiliconate-zeolite composites prepared in Example 1. The detergentcompositions were prepared by first forming a slurry of the followingcomposition:

    ______________________________________                                        800 g     Sodium salt of dodecylbenzenesulfonic acid                                    (60% solids)                                                        240 g     Sodium sulfate                                                      405 g     Sodium silicate solids (2.4 SiO.sub.2 /Na.sub.2 O)                  867 g     Anionic siliconate-zeolite composite                                400 g     Sodium carbonate                                                    2695 g    Water                                                               ______________________________________                                    

The slurries were spray dried utilizing a laboratory scale, rotary spraydryer. The conditions for drying were selected to provide about 6percent water in the final powdered product. The drying of theseslurries was free from problems and no agglomeration of the powders wasnoted during the processing. Detergent Compositions A, B, C and D wereprepared containing respectively uncoated Na-Zeolite A, zeolitecomposite I, zeolite composite II, and zeolite composite III, all asdescribed in Example 1. Detergent Composition A is outside the scope ofthis invention and is presented for comparison purposes only.

EXAMPLE 4

This example shows that the ion exchange capacity and rate of ionexchange for detergent compositions containing anionic siliconate coatedzeolites is not adversely affected in comparison to an equivalentdetergent formulation containing uncoated zeolite.

A 0.2 g portion of each detergent composition from Example 4 was addedto a 50 ml portion of a stock solution containing 272 ppm Ca⁺² ascalcium chloride. The detergent was mixed in the Ca⁺² containing waterfor precisely two minutes and the mixture was quickly filtered to removeall undissolved portions of the detergent powder. The filtrate wastitrated as in Example 2 and the amounts of Ca⁺² found remaining in thefiltrate is presented in Table 2.

                  TABLE 2                                                         ______________________________________                                        Calcium Ion Exchange Properties                                               of Powder Detergent Compositions                                                                        Amount of Ca.sup.+2                                                           Left After                                          Detergent                                                                              Anionic Siliconate-Zeolite                                                                     Detergent Treatment                                 Composition                                                                            Composite Used   (ppm)                                               ______________________________________                                        A (control)                                                                            Uncoated Na--Zeolite A                                                                         78                                                  B        I                56                                                  C        II               76                                                  D        III              60                                                  ______________________________________                                    

EXAMPLE 5

This example shows a comparison of the amount of agglomerated zeoliteparticles formed in detergent compositions of this invention andconventional detergent compositions.

The detergent compositions prepared in Example 3 were evaluated by ablack cloth test to determine the extent of zeolite agglomerateparticles that would be retained on fabric while laundering. For thetest, 0.75 g of the powder detergent composition was agitated for 10minutes in 1000 ml of deionized water with an impellor blade stirreroperating at 350 rpm. After agitation, the mixture was vacuum filteredthrough a 13 mm diameter piece of black broad cloth. After the cloth hadair dried, the reflectivity of the cloth was measured. A higherreflectivity corresponds to retention of a higher amount of whiteparticles on the black cloth. The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Black Cloth Test for Agglomerated Zeolite Particles                           Detergent  Anionic Siliconate-Zeolite                                         Composition                                                                              Composite Employed                                                                             Reflectivity                                      ______________________________________                                        A (control)                                                                              Uncoated Na--Zeolite A                                                                         51                                                B          I                 0                                                C          II                0                                                D          III              42                                                ______________________________________                                    

EXAMPLE 6

This example shows a comparison of the amount of agglomerated zeoliteparticles formed in detergent compositions of this inventon and adetergent composition containing zeolite treated withgamma-glycidoxypropyltrimethoxysilane.

Anionic siliconate-zeolite composites were prepared with various levelsof siliconate on the zeolite by the procedure described in Example 1.The composites were incorporated into a detergent formulation asdescribed in Example 3 using the rotary spray dryer. Drying conditionswere varied to provide two samples of each composition, one sample withabout 7 weight percent residual water and one with about 12 weightpercent residual water.

A comparison zeolite composite was prepared by first dissolvinggamma-glycidoxypropyltrimethoxysilane in an approximately equal amountof water that was acidified to pH 4 with HCl. This aqueous solution wasemployed to prepare a silane-zeolite composite by the same procedureused to form the siliconate-zeolite composites. This silane-zeolitecomposite was then incorporated into the same detergent formulation usedwith the siliconate-zeolite composites. These granular detergentcompositions were evaluated by the black cloth test as described inExample 5. Results are presented in Table 4.

                  TABLE 4                                                         ______________________________________                                        Black Cloth Test Comparison                                                   for Granular Detergent Compositions                                                                    Weight                                                                        Percent                                                            Weight     Residual  Reflectivity                                             Percent of Water     of                                         Zeolite       Siliconate on                                                                            in the    Black                                      Treatment     the Zeolite                                                                              Detergent Cloth                                      ______________________________________                                        None          0          6.7       16                                         None          0          8.3       24                                         Silane.sup.1  2          6.4       15                                         Silane.sup.1  2          11.8      2.4                                        Siliconate I.sup.2                                                                          4          5.8       13                                         Siliconate I.sup.2                                                                          4          11.4       0                                         Siliconate I.sup.2                                                                          2          7.6       19                                         Siliconate I.sup.2                                                                          2          12.9      2.0                                        Siliconate II.sup.2                                                                         2          6.6       15                                         Siliconate II.sup.2                                                                         2          11.5       0                                         Siliconate II.sup.2 + 2NaOH                                                                 2          7.0       1.5                                        Siliconate II.sup.2 + 2NaOH                                                                 2          11.5       0                                         ______________________________________                                         .sup.1 Gammaglycidoxypropyltrimethoxysilane                                   .sup.2 See Example 1 for general formulas                                

That which is claimed is:
 1. A detergent composition comprising(A) 5 to40 percent by weight of an organic surfactant selected from the groupconsisting of anionic, nonionic and ampholytic surfactants; (B) 1 to 50percent by weight of an anionic siliconate-zeolite composite containingzeolite with a surface coating of 0.1 to 10 percent by weight of anionicfunctional siliconate represented by the formula

    (MO).sub.a O.sub.(3-a)/2 Si--R--Y.sub.b

wherein Y represents an alkali metal salt of an oxyacid group, R is anorganic linking group wherein Y or other functionality selected from thegroup consisting of ether, sulfide, hydroxy, amide and amine ispositioned at least 2 carbon atoms removed from the silicon atom, a hasa value of from 1 to 3, b is an integer from 1 to 3, and M is an alkalimetal cation or hydrogen; and (C) 1 to 20 percent by weight of a watersoluble alkali metal silicate.
 2. The detergent composition of claim 1wherein the alkali metal salt of the oxyacid is selected from the groupconsisting of alkali metal salts of sulfonic acids, phosphonic acids,monoesters of phosphonic acids and carboxylic acids.
 3. The detergentcomposition of claim 2 wherein the organic linking grop, R, contains 2to 16 carbon atoms and is selected from the group consisting of radicalscomposed of carbon and hydrogen; radicals composed of carbon, hydrogenand oxygen; radicals composed of carbon, hydrogen and sulfur; andradicals composed of carbon, hydrogen and nitrogen.
 4. The detergentcomposition of claim 3 wherein b is 2 or
 3. 5. The detergent compositionof claim 4 wherein Y is an alkali metal salt of a carboxylic acid group.6. The detergent composition of claim 5 wherein R is a radical composedof carbon, hydrogen and nitrogen atoms.
 7. The detergent composition ofclaim 6 wherein the anionic functional siliconate is represented by theformula ##STR7## wherein M is hydrogen or sodium.
 8. The detergentcomposition of claim 6 wherein the anionic functional siliconate isrepresented by the formula ##STR8## wherein M is hydrogen or sodium. 9.The detergent composition of claim 3 wherein Y is the sodium salt of amonoester of phosphonic acid.
 10. The detergent composition of claim 9wherein the anionic functional siliconate is represented by the formula##STR9## wherein M is hydrogen or sodium.
 11. A composition consistingessentially of(A) 90 to 99.9 percent by weight of zeolite in the sodiumform, containing 15 to 35 percent water, and (B) coated on the surfaceof the zeolite, 0.1 to 10 percent by weight of anionic functionalsiliconate represented by the formula

    (MO).sub.a O.sub.(3-a)/2 Si--R--Y.sub.b

wherein Y represents an alkali metal salt of an oxyacid group, R is anorganic linking group wherein Y or other functionality selected from thegroup consisting of ether, sulfide, hydroxy, amide and amine ispositioned at least 2 carbon atoms removed from the silicon atom, a hasa value of from 1 to 3, b is an integer from 1 to 3, and M is an alkalimetal cation or hydrogen.
 12. The compositions of claim 11 wherein thealkali metal salt of the oxyacid is selected from the group consistingof alkali metal salts of sulfonic acids, phosphonic acids, monoesters orphosphonic acids and carboxylic acids.
 13. The composition of claim 12wherein the organic linking group, R, contains 2 to 16 carbon atoms andis selected from the group consisting of radicals composed of carbon andhydrogen; radicals composed of carbon, hydrogen and sulfur; radicalscomposed of carbon, hydrogen and oxygen; and radicals composed ofcarbon, hydrogen and nitrogen.
 14. The composition of claim 13 wherein bis 2 or 3 and Y is an alkali metal salt of a carboxylic acid group. 15.The composition of claim 14 wherein R is a radical composed of carbon,hydrogen and nitrogen atoms.
 16. The composition of claim 15 wherein theanionic functional siliconate is represented by the formula ##STR10##wherein M is hydrogen or sodium.
 17. The composition of claim 13 whereinY is the sodium salt of a monoester of phosphonic acid.
 18. Thecomposition of claim 17 wherein the anionic functional siliconate isrepresented by the formula ##STR11## wherein M is hydrogen or sodium.